CN114276510A - Zero free amine isocyanate modified aziridine crosslinking agent, and preparation method and application thereof - Google Patents
Zero free amine isocyanate modified aziridine crosslinking agent, and preparation method and application thereof Download PDFInfo
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- CN114276510A CN114276510A CN202210122327.0A CN202210122327A CN114276510A CN 114276510 A CN114276510 A CN 114276510A CN 202210122327 A CN202210122327 A CN 202210122327A CN 114276510 A CN114276510 A CN 114276510A
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- aziridine
- crosslinking agent
- free amine
- polyisocyanate
- ether
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 111
- 239000012948 isocyanate Substances 0.000 title claims abstract description 35
- -1 amine isocyanate modified aziridine Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 150000001412 amines Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 30
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 30
- 239000010985 leather Substances 0.000 claims abstract description 27
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 230000001681 protective effect Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004971 Cross linker Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001541 aziridines Chemical class 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 claims description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004069 aziridinyl group Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 11
- 230000004913 activation Effects 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 48
- 239000004925 Acrylic resin Substances 0.000 description 16
- 229920000178 Acrylic resin Polymers 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 238000004043 dyeing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229920002873 Polyethylenimine Polymers 0.000 description 2
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- 206010010071 Coma Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a zero free amine isocyanate modified aziridine crosslinking agent, and a preparation method and application thereof, and belongs to the field of polyurethane curing agents. The invention leads aziridine monomer and monomer containing epoxy group to carry out ring-opening reaction, and then diisocyanate is added to react for 4h-6h at the temperature of-20 ℃ to 0 ℃ to obtain an intermediate. And adding polyethylene glycol monomethyl ether into polyisocyanate, dropwise adding the intermediate after the polyisocyanate and the polyethylene glycol monomethyl ether completely react, and adding a solvent to dilute to a certain viscosity to obtain the cross-linking agent. The content of free amine in the product of the invention is below 10ppm, and the defects of short activation period, high content of free amine and low crosslinking density of the existing aziridine crosslinking agent are overcome. The cross-linking agent is added into the acrylic emulsion and the polyurethane emulsion, so that the cross-linking density can be obviously improved, the adhesion of a coating film is improved, and the water resistance and chemical resistance of the coating film are enhanced. Because the cross-linking agent does not contain free amine, the cross-linking agent can be widely applied to the fields of high-grade woodware, leather finishing, water-based paint and the like.
Description
Technical Field
The invention belongs to the field of polyurethane curing agents, and particularly relates to a zero free amine isocyanate modified aziridine crosslinking agent, and a preparation method and application thereof.
Background
The waterborne polyurethane emulsion has the advantages of strong adjustability of molecular structure, good hand feeling, strong adhesive force, wear resistance, no hot stickiness, no cold brittleness and the like, so that the waterborne polyurethane emulsion is widely applied to the fields of coatings and the like. However, because the molecular weight is relatively small, the molecular structure is embedded with a hydrophilic chain segment, and the performances of water resistance, solvent resistance and the like are poor; the acrylic emulsion is widely applied to the field of coatings due to excellent film forming property, good transparency, excellent mechanical property and environmental protection property; however, the molecules are mostly linear structures and lack crosslinking points, so that the water resistance, weather resistance and heat resistance are poor (namely, hot-sticking and cold-brittleness), and the application range is influenced.
The application publication numbers of CN102985449A, CN108084771A, CN10478872A, CN104478776A and CN111960982A relate to the synthesis of a trifunctional aziridine crosslinking agent by taking TMPTA, methylaziridine and the like as raw materials, and 1 to 5 percent of the crosslinking agent is added into polyurethane and acrylic emulsion to be applied to a protective film, so that the surface tension can be reduced, and the coating residual gum can be effectively prevented; the adhesive is applied to the fields of printing and leather, and can effectively improve the adhesive force and the wet wiping resistance. However, the aziridine crosslinking agent prepared by the method has short activation period, poor hand feeling and high content of free amine, and the application of the aziridine crosslinking agent is severely limited.
Free amine is mainly aziridine monomer, and due to low boiling point, small molecular weight and high toxicity, the free amine not only seriously affects the health of people, but also causes coma or death due to skin allergy, molting and excessive inhalation of mild people; the numerous disadvantages of the presence of incompletely reacted aziridines as free amines in the crosslinking agents limit their range of application.
Patent application publication No. CN112225878A, CN107828049A, which relates to isocyanate modified aziridine crosslinking agent obtained by reacting HDI trimer and methyl aziridine, but does not solve the problem of high content of free amine at all, and introduces hydrophilic chain extension, resulting in decrease of average functionality, and crosslinking effect is not even better than that of conventional aziridine crosslinking agent, patent application publication No. CN112469755A synthesizes a polyaziridine compound, which treats excess free amine by reduced pressure distillation, but this method is excessive in aziridine, distillation of aziridine at later stage is not only energy-consuming, aziridine recovery is also a problem, and the average functionality of the synthesized polyaziridine crosslinking agent is also lower than 3, and crosslinking density is decreased. Therefore, the development of the aziridine crosslinking agent with low free amine content and high crosslinking density has research and application values.
Disclosure of Invention
The invention provides a preparation method of a zero free amine isocyanate modified aziridine crosslinking agent, and aims to overcome the defects of short activation period, poor hand feeling, high free amine content and low crosslinking density of an aziridine crosslinking agent in the prior art.
In view of the above technical drawbacks, an object of the present invention is to provide a method for preparing a zero free amine isocyanate modified aziridine crosslinking agent, a second object of the present invention is to provide a crosslinking agent prepared by the method for preparing the zero free amine isocyanate modified aziridine crosslinking agent, and a third object of the present invention is to provide the use of the isocyanate modified aziridine crosslinking agent as a crosslinking agent in the production of protective films, leather finishing, and base fabric printing.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a zero free amine isocyanate modified aziridine crosslinking agent, comprising the steps of:
(1) preparation of an intermediate: dripping an aziridine monomer and a catalyst into an epoxy monomer compound, preserving heat after dripping is finished, adding diisocyanate (such as TDI) and reacting at-20-0 ℃ (for example, -18 ℃, 15 ℃, 10 ℃, 8 ℃ and 5 ℃) when the mass content of the unreacted aziridine monomer in a reaction system is detected to be lower than 1%, and taking the obtained product as an intermediate when the mass content of free aziridine in the reaction system is detected to be lower than 10ppm or the free aziridine is not detected;
(2) preparation of isocyanate-modified aziridine crosslinker: and adding polyethylene glycol monomethyl ether into polyisocyanate, heating, keeping the temperature, dropwise adding the intermediate after the polyisocyanate and the polyethylene glycol monomethyl ether completely react, adding a solvent for dilution, and keeping the temperature to obtain the zero-free amine isocyanate modified aziridine crosslinking agent.
The method of judging the completion of the reaction of the polyisocyanate with the polyethylene glycol monomethyl ether in the step (2) of the production method of the present invention is judged by detecting whether the percentage NCO% by mass of NCO (isocyanate group) in the reaction of the polyisocyanate to the initial mass of NCO (isocyanate group) in the polyisocyanate falls to a theoretical value (theoretical end point value). When the NCO% is reduced to a theoretical value, which indicates that the reaction is complete, the intermediate can be further dripped, so that the intermediate and NCO which is not reacted with the polyethylene glycol monomethyl ether in the polyisocyanate undergo further reaction. Due to the different reactivity of NCO at different positions on polyisocyanate, not all NCO on polyisocyanate reacts with hydroxyl on methoxy polyethylene glycol. The theoretical value (theoretical end point value) is the percentage of the mass of the residual NCO on the polyisocyanate which is not reacted with the polyethylene glycol monomethyl ether to the initial mass of NCO on the polyisocyanate after the reaction is theoretically completed, calculated according to the mole number of NCO which can react with the hydroxyl group of the polyethylene glycol monomethyl ether on the polyisocyanate used as the raw material.
In the above production method, as a preferred embodiment, the crosslinking agent has a free amine content of less than 10 ppm; preferably, the crosslinking agent is free of free amine as determined by gas chromatography; preferably, the cross-linking agent has a viscosity of 400 to 700 mpa.s; preferably the cross-linking agent has a viscosity of 477 to 667 mpa.s.
The function of adding the solvent in the step (2) of the preparation method is to dilute, and the free amine is unreacted aziridine monomer compound. The polyisocyanates referred to herein are those having a functionality of greater than 2. The technical principle of the invention is as follows: the method adopts aziridine and epoxy monomer to carry out ring opening, and the aziridine and the epoxy monomer carry out esterification reaction with isocyanate to obtain an isocyanate modified aziridine crosslinking agent; the zero free amine is achieved by removing unreacted aziridine monomer by high reactivity with aziridine at low temperature using small molecular diisocyanates.
In the above preparation method, as a preferred embodiment, the solvent is added in the step (2) to dilute so that the solid content of the crosslinking agent is 75 wt% to 95 wt% (e.g., 80 wt%, 85 wt%, 90 wt%); preferably, the continuous heat preservation refers to that the heat preservation is continued until the percentage of the mass of NCO in the polyisocyanate in the reaction system to the initial mass of NCO in the polyisocyanate in the raw materials is less than 0.5 percent after the solvent is added for dilution.
In step (2) of the present invention, the NCO% is controlled to be less than 0.5% to confirm completion of the reaction.
In the above preparation method, as a preferred embodiment, the total weight of the raw material epoxy monomer compound, aziridine monomer, catalyst, diisocyanate, polyisocyanate, polyethylene glycol monomethyl ether and solvent for preparing the cross-linking agent is calculated, wherein the epoxy monomer compound is used in an amount of 10 wt% to 30 wt%; preferably, the aziridine monomer is used in an amount of 5 wt% to 15 wt% (e.g., 8 wt%, 10 wt%, 12 wt%, 14 wt%); preferably, the catalyst is used in an amount of 0.2 wt% to 0.5 wt% (e.g., 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%); preferably, the diisocyanate is used in an amount of 1 wt% to 5 wt% (e.g., 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%); preferably, the polyisocyanate is used in an amount of 20 wt% to 40 wt% (e.g., 25 wt%, 27.5 wt%, 30 wt%, 32.5 wt%, 35 wt%, 37.5 wt%); preferably, the polyethylene glycol monomethyl ether is used in an amount of 5 wt% to 15 wt% (e.g., 7.5 wt%, 10 wt%, 12.5 wt%); preferably, the solvent is used in an amount of 5 wt% to 20 wt% (e.g., 7.5 wt%, 10 wt%, 12.5 wt%, 15 wt%, 17.5 wt%).
In the above-mentioned production method, as a preferable embodiment, in the step (1), the epoxy monomer compound is heated to 30 ℃ to 50 ℃ (for example, 35 ℃, 40 ℃, 45 ℃), and the aziridine monomer and the catalyst are added dropwise; preferably, the incubation temperature in step (1) is from 40 ℃ to 60 ℃ (e.g., 45 ℃, 50 ℃, 55 ℃); preferably, the temperature keeping time in the step (1) is 20h-50h (such as 25h, 30h, 35h, 40h and 45 h); further preferably, the heat preservation time in the step (1) is 40 h; preferably, the reaction time after the diisocyanate is added in step (1) is 4h to 6h (e.g. 4.5h, 5h, 5.5h) at-20 ℃ to 0 ℃ (e.g. -18 ℃, -15 ℃, -10 ℃, -8 ℃, -5 ℃).
In the above production method, as a preferable embodiment, the temperature for the heat preservation in the step (2) is 50 to 80 ℃ (e.g., 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃); preferably, the heat preservation time in the step (2) is 2h-5 h; further preferably, the heat preservation time in step (2) is 3 h.
In the above production process, as a preferable embodiment, the temperature of the intermediate added dropwise in the step (2) is 50 ℃ to 70 ℃ (e.g., 55 ℃, 60 ℃, 65 ℃); further preferably, the temperature of the dropwise adding intermediate in the step (2) is 60 ℃; preferably, the time for dropping the intermediate in the step (2) is 1h-3h (e.g. 1.5h, 2h, 2.5 h); further preferably, the time for dropping the intermediate in the step (2) is 2 hours.
In the above production method, as a preferred embodiment, the intermediate is a hydroxy group-containing aziridine compound; preferably, the structure of the intermediate is shown as formula II or formula III; preferably, in the intermediate, R1, R2, R3 and R4 are all alkyl groups, and R1, R2, R3 and R4 are the same or different, and more preferably all alkyl groups having 1 to 10 carbons.
In the above production method, as a preferable embodiment, the epoxy monomer compound is at least one of bisphenol a epoxy resin, trimethylolpropane triglycidyl ether, n-butyl glycidyl ether, polypropylene glycol diglycidyl ether, allyl glycidyl ether, isopropyl glycidyl ether, butanediol diglycidyl ether, and ethylene glycol diglycidyl ether.
In the above production method, as a preferred embodiment, the aziridine-based monomer is aziridine and/or methylaziridine.
In the above production method, as a preferable embodiment, the diisocyanate is TDI, HDI or IPDI; TDI is more preferable.
In the selection of the diisocyanate, the potential difference between C, N atoms in-NCO groups in molecules is increased due to the strong electron withdrawing effect of TDI six-membered rings, the reactivity is increased, and the reaction speed is accelerated, so that the effect of removing unreacted aziridine monomers by using TDI and aziridine through high-activity reaction at low temperature is better.
In the above production method, as a preferable embodiment, the polyisocyanate is an isocyanate having an average functionality of more than 2.
In the above production method, as a preferable embodiment, the polyisocyanate is a HDI trimer, TDI-TMP adduct, isophorone diisocyanate trimer (IPDI trimer) or toluene diisocyanate trimer (TDI trimer).
The polyisocyanate of the present invention refers to isocyanate with functionality greater than 2, and the isocyanate with functionality greater than 2 can be used as the polyisocyanate of the present invention to participate in the reaction.
In the above preparation method, as a preferred embodiment, the weight average molecular weight of the polyethylene glycol monomethyl ether is selected to be between 200-1000.
In the above production method, as a preferable embodiment, the solvent is propylene glycol methyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol methyl ether, propylene glycol monomethyl ether, propylene glycol butyl ether or ethylene glycol butyl ether.
In the above preparation method, as a preferred embodiment, the catalyst is cesium carbonate, potassium carbonate, triethylamine, potassium hydroxide or sodium hydroxide.
In a second aspect, the present invention provides an isocyanate-modified aziridine crosslinking agent prepared by the above preparation process.
In a third aspect, the present invention provides the use of the isocyanate-modified aziridine crosslinking agent as a crosslinking agent in the production of protective films, leather finishing and base printing.
Compared with the prior art, the invention has the following beneficial effects:
the aziridine crosslinking agent synthesized by the invention is detected by a third party, free amine is not detected or is lower than the minimum limit of 10ppm, and the free amine of similar products in the market is between 200 and 3000ppm, so that the zero free amine can be widely used in high-grade woodware, textile, printing ink and water-based paint, the crosslinking density of a coating film is improved, and the adhesive force is enhanced. In the preparation process of the intermediate, the invention utilizes the strong reactivity of the low molecular weight diisocyanate and the aziridine monomer under the low temperature condition to remove free amine, thereby fundamentally solving the problem of free amine in the cross-linking agent, and also introduces the bifunctional epoxy monomer, thereby increasing the cross-linking density and solving the problems of low cross-linking density of the cross-linking agent, surface coating defects caused by shrinkage and the like.
Detailed Description
The process for preparing the zero free amine isocyanate modified aziridine crosslinking agent according to the invention is described in further detail below with reference to specific embodiments, which are given by way of illustration only and are not intended to limit the scope of the invention. The following examples are provided as the basis for further modifications and applications by those skilled in the art and are not to be construed as limiting the invention in any way.
In the detection of the application performance of the cross-linking agent in the embodiment of the invention, in the test of dyeing and printing rubbing color fastness, the test of dyeing and printing washing color fastness and the test of leather rubbing color fastness, the representation of the detection result takes more than or equal to 1000 times as an example, namely, the performance of the sample is reduced after 1000 times of wiping.
Example 1
Preparing an intermediate: accurately weighing 10g of n-butyl glycidyl ether and 3g of ethylene glycol diglycidyl ether, heating to 40 ℃, dropwise adding 8g of methyl aziridine and 0.3g of potassium carbonate, reacting at 60 ℃ for 40h to obtain a reaction system, measuring the mass content of the methyl aziridine in the reaction system to be less than or equal to 1%, adding 2g of TDI, keeping the temperature at-20 ℃ for 4h, and detecting that no free amine is detected by gas chromatography to obtain 23.3g of an intermediate.
Preparation of a zero free amine isocyanate modified aziridine crosslinking agent: weighing 20g of HDI trimer, dropwise adding 8g of polyethylene glycol monomethyl ether with the molecular weight of 500, keeping the reaction temperature at 60 ℃, keeping the temperature for 2h, measuring that NCO% (the mass percentage of isocyanate groups in a reaction system to initial isocyanate groups) is 15.6% (theoretical value), then dropwise adding 23.3g of intermediate at 60 ℃ for 2h, adding 10g of propylene glycol methyl ether acetate, diluting, keeping the temperature for 3h, measuring that NCO% is less than 0.5%, confirming that the reaction is finished, cooling to room temperature, discharging, obtaining the isocyanate modified aziridine crosslinking agent without free amine, and detecting no free amine and the viscosity of the crosslinking agent is 567mPa.
The application comprises the following steps:
applied to the field of protective films: weighing 100g of Baolijia BLJ-538 acrylic resin emulsion, adding 1 wt% (relative to the mass of the acrylic resin emulsion) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for diluting, uniformly spraying on a protective film by using a spray gun, drying for 3min, baking for 3min at 105 ℃, and cooling for later use;
the method is applied to the field of leather finishing: weighing 100g of matte resin Leasys3978, adding 3 wt% (relative to the mass of the matte resin Leasys 3978) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for dilution, uniformly spraying the mixture on the surface of leather by using a spray gun, baking for 3min at 105 ℃, and cooling for later use;
be applied to the printing field: 100g of nylon-tay printing paste acrylic resin 8073 was weighed, 3 wt% (based on the mass of the acrylic resin 8073) of the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was added, 5g of a color paste was added, the mixture was stirred uniformly, the mixture was coated uniformly on a white base fabric with a squeegee, baked at 80 ℃ for 20 minutes, and cooled for use.
Application test performance:
the protective film, leather and printed base fabric, to which the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was applied, respectively, were subjected to a protective film peel force test, a printing and dyeing rubbing fastness test, a printing and dyeing washing fastness test or a leather rubbing fastness test, and the test results are shown in tables 1, 2 and 3 below.
Table 1 protective film peel force test
TABLE 2 rubbing fastness test, washing fastness test for printing and dyeing
TABLE 3 leather color fastness to rubbing test
As can be seen by comparing the test data in tables 1, 2 and 3, the isocyanate modified aziridine crosslinking agent begins to deteriorate in the dye printing rubbing color fastness test and the washing color fastness test when the sample using the conventional crosslinking agent is dry rubbed more than or equal to 20 or wet rubbed more than or equal to 20, and when the sample using the isocyanate modified aziridine crosslinking agent is dry rubbed more than or equal to 50 or wet rubbed more than or equal to 30. And the activation period of the isocyanate modified aziridine crosslinking agent is 15d which is far longer than that of the traditional crosslinking agent by 6h, so that the isocyanate modified aziridine crosslinking agent has the fastness obviously superior to that of the traditional CX-100 crosslinking agent and the content of free amine which is far lower than that of the traditional aziridine crosslinking agent.
Example 2
Preparing an intermediate: accurately weighing 10g of n-butyl glycidyl ether and 3g of ethylene glycol diglycidyl ether, heating to 40 ℃, dropwise adding 10g of aziridine and 0.3g of potassium carbonate, reacting at 60 ℃ for 40h to obtain a reaction system, measuring that the mass content of the aziridine in the reaction system is less than or equal to 1%, adding 2g of TDI, keeping the temperature at-20 ℃ for 4h, and detecting that free amine is not detected by gas chromatography to obtain 25.3g of an intermediate.
Preparation of a zero free amine isocyanate modified aziridine crosslinking agent: weighing 20g of HDI trimer, dropwise adding 8g of polyethylene glycol monomethyl ether with the molecular weight of 500, keeping the reaction temperature at 60 ℃, keeping the temperature for 2h, measuring that NCO% (the mass percentage of isocyanate groups in a reaction system to initial isocyanate groups) is 14.3% (theoretical value), dropwise adding 25.3g of intermediate at 60 ℃ for 2h, adding 10g of propylene glycol methyl ether acetate, diluting, keeping the temperature for 3h, determining that the NCO% is less than 0.5%, confirming that the reaction is finished, cooling to room temperature, discharging, and obtaining the isocyanate modified aziridine crosslinking agent without free amine. No free amine was detected by GC, the crosslinker viscosity 667 mpa.s.
The application comprises the following steps:
applied to the field of protective films: weighing 100g of Baolijia BLJ-538 acrylic resin emulsion, adding 1 wt% (relative to the mass of the acrylic resin emulsion) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for diluting, uniformly spraying on a protective film by using a spray gun, drying for 3min, baking for 3min at 105 ℃, and cooling for later use;
the method is applied to the field of leather finishing: weighing 100g of matte resin Leasys3978, adding 3 wt% (relative to the mass of the matte resin Leasys 3978) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for dilution, uniformly spraying the mixture on the surface of leather by using a spray gun, baking for 3min at 105 ℃, and cooling for later use;
be applied to the printing field: 100g of nylon-tay printing paste acrylic resin 8073 was weighed, 3 wt% (based on the mass of the acrylic resin 8073) of the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was added, 5g of a color paste was added, the mixture was stirred uniformly, the mixture was coated uniformly on a white base fabric with a squeegee, baked at 80 ℃ for 20 minutes, and cooled for use.
Application test performance:
the protective film, leather and printed base fabric, to which the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was applied, respectively, were subjected to a protective film peel force test, a printing and dyeing rubbing fastness test, a printing and dyeing washing fastness test or a leather rubbing fastness test, and the test results are shown in tables 4, 5 and 6 below.
Table 4 protective film peel force test
TABLE 5 rubbing fastness test, washing fastness test for printing and dyeing
TABLE 6 leather crocking fastness test
As can be seen by comparing the test data in tables 1-3 and 4, and tables 5 and 6, the activation period of the aziridine crosslinking agent is 20d, which is significantly higher than the activation period of the methyl aziridine crosslinking agent of 15d, and the application properties of the aziridine crosslinking agent are not much different, but both of them are better than that of the conventional crosslinking agent CX-100.
Example 3
Preparing an intermediate: accurately weighing 12g of n-butyl glycidyl ether and 3g of ethylene glycol diglycidyl ether, heating to 40 ℃, dropwise adding 8g of methyl aziridine and 0.3g of potassium carbonate, reacting at 60 ℃ for 40h to obtain a reaction system, measuring the mass content of the methyl aziridine in the reaction system to be less than or equal to 1%, adding 2g of TDI, keeping the temperature at-20 ℃ for 4h, and detecting that no free amine is detected by gas chromatography to obtain 25.3g of an intermediate.
Preparation of a zero free amine isocyanate modified aziridine crosslinking agent: weighing 20g of TDI-TMP addition product, dropwise adding 8g of polyethylene glycol monomethyl ether with the molecular weight of 500, keeping the temperature at 60 ℃, keeping the temperature for 2h, measuring that NCO% (the mass percentage of isocyanate groups in a reaction system to initial isocyanate groups) is 16.3% (theoretical value), dropwise adding 25.3g of intermediate at 60 ℃ for 2h, adding 10g of propylene glycol monomethyl ether for dilution, keeping the temperature for 3h, measuring that NCO% is less than 0.5%, confirming that the reaction is finished, cooling to room temperature, discharging, and obtaining the isocyanate modified aziridine crosslinking agent without free amine. No free amine was detected by GC and the crosslinker viscosity was 527 mpa.s.
The application comprises the following steps:
applied to the field of protective films: weighing 100g of Baolijia BLJ-538 acrylic resin emulsion, adding 1 wt% (relative to the mass of the acrylic resin emulsion) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for diluting, uniformly spraying on a protective film by using a spray gun, drying for 3min, baking for 3min at 105 ℃, and cooling for later use;
the method is applied to the field of leather finishing: weighing 100g of matte resin Leasys3978, adding 3 wt% (relative to the mass of the matte resin Leasys 3978) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for dilution, uniformly spraying the mixture on the surface of leather by using a spray gun, baking for 3min at 105 ℃, and cooling for later use;
be applied to the printing field: 100g of nylon-tay printing paste acrylic resin 8073 was weighed, 3 wt% (based on the mass of the acrylic resin 8073) of the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was added, 5g of a color paste was added, the mixture was stirred uniformly, the mixture was coated uniformly on a white base fabric with a squeegee, baked at 80 ℃ for 20 minutes, and cooled for use.
Application test performance:
the protective film, leather and printed base fabric, to which the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was applied, respectively, were subjected to a protective film peel force test, a printing and dyeing rubbing fastness test, a printing and dyeing washing fastness test or a leather rubbing fastness test, and the test results are shown in tables 7, 8 and 9 below.
Table 7 protective film peel force test
TABLE 8 rubbing fastness test, washing fastness test for printing and dyeing
TABLE 9 leather rub fastness test
As can be seen by comparing the test data in tables 1-3 and tables 7-9 above, the isocyanate modified aziridine crosslinking agent prepared using TDI-TMP of this example performed better than the conventional crosslinking agent CX-100, but not as well as the isocyanate modified aziridine crosslinking agent prepared using HDI trimer.
Example 4
Preparation of intermediate 1: accurately weighing 15g of n-butyl glycidyl ether, heating to 40 ℃, then dropwise adding 8g of methyl aziridine and 0.3g of potassium carbonate, reacting for 40h at 60 ℃, measuring that the mass content of the methyl aziridine in the reaction system is less than or equal to 1%, adding 2g of TDI, keeping the temperature at-20 ℃ for 4h, and measuring that free amine is not detected by gas chromatography to obtain 25.3g of an intermediate.
Preparation of a zero free amine isocyanate modified aziridine crosslinking agent: weighing 20g of HDI trimer, dropwise adding 8g of polyethylene glycol monomethyl ether with the molecular weight of 500, keeping the reaction temperature at 60 ℃, keeping the temperature for 2h, measuring that NCO% (the mass percentage of isocyanate groups in a reaction system to initial isocyanate groups) is 14.6% (theoretical value), dropwise adding 25.3g of intermediate at 60 ℃ for 2h, adding 10g of propylene glycol methyl ether for dilution, keeping the temperature for 3h, measuring that NCO% is less than 0.5%, confirming that the reaction is finished, cooling to room temperature, discharging, and obtaining the isocyanate modified aziridine crosslinking agent without free amine. No free amine was detected by GC, cross-linker viscosity 477 mpa.s.
The application comprises the following steps:
applied to the field of protective films: weighing 100g of Baolijia BLJ-538 acrylic resin emulsion, adding 1 wt% (relative to the mass of the acrylic resin emulsion) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for diluting, uniformly spraying on a protective film by using a spray gun, drying for 3min, baking for 3min at 105 ℃, and cooling for later use;
the method is applied to the field of leather finishing: weighing 100g of matte resin Leasys3978, adding 3 wt% (relative to the mass of the matte resin Leasys 3978) of aziridine crosslinking agent or traditional crosslinking agent CX-100 prepared in the embodiment, uniformly stirring, adding 20g of deionized water for dilution, uniformly spraying the mixture on the surface of leather by using a spray gun, baking for 3min at 105 ℃, and cooling for later use;
be applied to the printing field: 100g of nylon-tay printing paste acrylic resin 8073 was weighed, 3 wt% (based on the mass of the acrylic resin 8073) of the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was added, 5g of a color paste was added, the mixture was stirred uniformly, the mixture was coated uniformly on a white base fabric with a squeegee, baked at 80 ℃ for 20 minutes, and cooled for use.
Application test performance:
the protective film, leather and printed base fabric, to which the aziridine crosslinking agent or the conventional crosslinking agent CX-100 prepared in this example was applied, respectively, were subjected to a protective film peel force test, a printing and dyeing rubbing fastness test, a printing and dyeing washing fastness test or a leather rubbing fastness test, and the test results are shown in tables 10, 11 and 12 below.
Table 10 protective film peel force test
TABLE 11 rubbing fastness test, Wash fastness test for printing and dyeing
TABLE 12 leather crocking fastness test
As can be seen from the data in tables 1 to 12, when the crosslinking agent prepared by the embodiment of the invention is applied to the fields of protective films, leather and printing, the performance is better than that of the conventional crosslinking agent CX-100, and free amine is not generated. Solves the defects of short activation period, poor hand feeling, high free amine content and low crosslinking density of the aziridine crosslinking agent in the prior art.
Claims (10)
1. A method for preparing a zero free amine isocyanate modified aziridine crosslinking agent, comprising the steps of:
(1) preparation of an intermediate: dripping an aziridine monomer and a catalyst into an epoxy monomer compound, preserving heat after dripping is finished, adding diisocyanate and reacting at-20-0 ℃ when the mass content of the unreacted aziridine monomer in a reaction system is detected to be lower than 1%, and taking the obtained product as an intermediate when the mass content of free aziridine in the reaction system is detected to be lower than 10ppm or free aziridine is not detected;
(2) preparation of isocyanate-modified aziridine crosslinker: and adding polyethylene glycol monomethyl ether into polyisocyanate, heating, keeping the temperature, dropwise adding the intermediate after the polyisocyanate and the polyethylene glycol monomethyl ether completely react, adding a solvent for dilution, and keeping the temperature to obtain the zero-free amine isocyanate modified aziridine crosslinking agent.
2. The method of claim 1, wherein the crosslinker has a free amine content of less than 10 ppm; preferably, the crosslinking agent is free of free amine as determined by gas chromatography; preferably, the cross-linking agent has a viscosity of 400 to 700 mpa.s; preferably the cross-linking agent has a viscosity of 477 to 667 mpa.s.
3. The method according to claim 1 or 2, wherein the crosslinking agent has a solid content of 75 to 95 wt% by diluting with a solvent in the step (2); preferably, the continuous heat preservation refers to that the heat preservation is continued until the percentage of the mass of NCO in the polyisocyanate in the reaction system to the initial mass of NCO in the polyisocyanate in the raw materials is less than 0.5 percent after the solvent is added for dilution.
4. The method of claim 1 or 2, wherein the epoxy monomer compound is used in an amount of 10 wt% to 30 wt%, based on the total weight of the raw epoxy monomer compound, aziridine monomer, catalyst, diisocyanate, polyisocyanate, polyethylene glycol monomethyl ether and solvent for preparing the crosslinking agent; preferably, the aziridine monomer is used in an amount of 5 wt% to 15 wt%; preferably, the catalyst is used in an amount of 0.2 wt% to 0.5 wt%; preferably, the diisocyanate is used in an amount of 1 to 5 wt%; preferably, the polyisocyanate is used in an amount of 20 wt% to 40 wt%; preferably, the amount of the polyethylene glycol monomethyl ether is 5-15 wt%; preferably, the solvent is used in an amount of 5 wt% to 20 wt%.
5. The method according to any one of claims 1 to 4, wherein in the step (1), the epoxy monomer compound is heated to 30 ℃ to 50 ℃, and the aziridine monomer and the catalyst are added dropwise; preferably, the heat preservation temperature in the step (1) is 40-60 ℃; preferably, the heat preservation time in the step (1) is 20h-50 h; further preferably, the heat preservation time in the step (1) is 40 h; preferably, the reaction time is 4-6 h at-20-0 ℃ after the diisocyanate is added in the step (1); preferably, the temperature in the step (2) is kept between 50 and 80 ℃; preferably, the heat preservation time in the step (2) is 2h-5 h; further preferably, the heat preservation time in the step (2) is 3 h; preferably, the temperature of the dropwise adding intermediate in the step (2) is 50-70 ℃; further preferably, the temperature of the dropwise adding intermediate in the step (2) is 60 ℃; preferably, the time for dripping the intermediate in the step (2) is 1h-3 h; further preferably, the time for dropping the intermediate in the step (2) is 2 hours.
6. The process according to any one of claims 1 to 5, wherein the intermediate is a hydroxy-containing aziridine compound; preferably, the structure of the intermediate is shown as formula II or formula III; preferably, in the intermediate, R1, R2, R3 and R4 are all alkyl groups, R1, R2, R3 and R4 are the same or different, more preferably all alkyl groups containing 1 to 10 carbons,
7. the method according to any one of claims 1 to 5, wherein the epoxy monomer compound is at least one of bisphenol A epoxy resin, trimethylolpropane triglycidyl ether, n-butyl glycidyl ether, polypropylene glycol diglycidyl ether, allyl glycidyl ether, isopropyl glycidyl ether, butanediol diglycidyl ether, and ethylene glycol diglycidyl ether.
8. The method according to any one of claims 1 to 7, wherein the aziridine-based monomer is an aziridine and/or a methyl aziridine; preferably, the diisocyanate is TDI, HDI or IPDI; further preferably TDI; preferably, the polyisocyanate is an isocyanate having an average functionality greater than 2; preferably, the polyisocyanate is an HDI trimer, TDI-TMP adduct, IPDI trimer or TDI trimer; preferably, the chosen polyethylene glycol monomethyl ether has a weight average molecular weight of between 200-1000; preferably, the solvent is propylene glycol methyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol methyl ether, propylene glycol monomethyl ether, propylene glycol butyl ether or ethylene glycol butyl ether; preferably, the catalyst is cesium carbonate, potassium carbonate, triethylamine, potassium hydroxide or sodium hydroxide.
9. An isocyanate-modified aziridine crosslinking agent, obtainable by a process as claimed in any of claims 1 to 8.
10. Use of the isocyanate modified aziridine crosslinking agent as claimed in claim 9 as a crosslinking agent in the production of protective films, leather finishing and base printing.
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